Composition comprising a vinyl chloride polymer plasticized with a mixture of chlorinated n, n-dialkylstearamides



United States Patent COMPOSITION COMPRISING A VINYLTCHLORIDE POLYMERPLASTICIZED WITH A MIXTURE OF CHLORINATED N,N DIALKYLSTEARAMIDES'Joachim Dazzi, Dayton, Ohio, assignor to Monsanto "Chemical Company, St.Louis, Mo., a corporation of Delaware No Drawing. Original applicationJan. 25; 19 54','S'er. No.- 406,070. Divided and this application May 8,1958, Ser. No. 733,839

4 Claims. c1'..z60,-32.6

The present invention relates to resinous compositions, and moreparticularly provides vinyl chloride polymers plasticized withchlorine-substituted N,N- dialkylstear-- amides having from two tofourchlorine atoms inthe fatty acid portion of the molecule, and having from1 to 5 carbon atoms in each N-alkyl radical.

The presently useful chloro compounds are readily reaction oflinoleamide With four atoms of chlorine gives theN,N-dialkyl-9,l0,12,13-tetrachlorostearamide:" Even though theN,N-dialkyloleamide or the N,N-dialkyllinole-- amide is contacted withmore than enough moles of chlorine for saturation of the olefinic doublebonds, substan-- tially no substitution of chlorine for hydrogen takesplace at ordinary or moderately increased temperatures, i.e., attemperatures of, say, below 100 C. At higher temperatures, introductionof chlorine in excess of that stoichiometrically required for saturationof the olefinic double bonds of the amides will result in replacementby' chlorine of the hydrogen atoms of the initially formedN,N-dialkyldichlorostearamides or the N,'N dialkyltetr-a--chlorostearamides.

Examples of the presently useful chlorine-additioncompounds areN,N-dimethyl-, N,N-diethyl N,N'-di'-npropy1'-,, N,N-diisobutyl-, orN,N-di-n-amyldichlorostearamide prepared by passing elemental chlorineinto N, N dimethyl-, N,N-diethyl-, N,N-di-n-propyl'-, N,N-diiso--butyl-, or N,N-di-n-arnyloleamide, respectively, or the correspondingN-dialkylated tetrachlorostearamides, e.g., N,N-dimethyl-,N,N-diisopropyl-, or N,N-did-tert-amyltetrachlorostearamide, prepared bypassing chlorine into- N,Ni-dimethyl- N,N-diisopropyl-, orNjN-di-tert-amyh linoleamide, respectively. The N,N-dialkyloleamides orthe N,N-dialkyllinoleamides are readily obtainable compounds prepared inknown manner, by condensation of oleic or linoleic acid or the acidhalides thereof with an appropriate dialkylamine, e.g., dimethylamine,dibutylamine or diamylamine. Particularly valuable for the presentpurposes are technical mixtures containing apredominant proportion ofthe N,N-dialkylamides of a mixture of oleic acid and linoleic acid,e.g., the unsaturated higher fatty acids derived from tall oil. n

The addition reaction takes place readily at decreased, ordinary ormoderately increased temperatures, say at temperatures of from- 0* Q.to- 1 00= G. and in the presence or absence of catalysts. Inasmuch asthe reaction is 2; exothermal, extraneous heating is generallyunnecessary; on the other hand, the heat evolved in the additionreaction is of so law an order that usually no precaution need beemployed for dissipating exothermal heat. Catalysts which may beemployed are metals, metal oxides and metallic salts such as iron,aluminum, iron oxides, cupric, ferric or calcium chloride, etc. Lightaccelerates addition of chlorine to the olefinic double bondsv of theN,N-diallryloleamide or N,N-dialkyllinoleamide. Hence, the halogenationis advantageously carried out in daylight or by use of an ultra-violetlight source. The photochlorination may be further accelerated by usingtheabove-mentioned catalysts. As hereinbefore stated, however, theaddition of chlorine to the olefinic double bonds, takes place so easilythat neither light or catalyst need" be employed in eifecting saturationof the double bond. Irrespective of the quantity of chlorine with whichthe N,N-dialkyl0leamide or the N,N-dialkyllinoleamide is contacted,within the lower temperature range, i.e., at a temperature of from say,0? C. to. C., from thesereactants there are formed predominantly the.N,N-dialkyl,- dichlorostearamides or theN,N-dialkyltetrachlorostearamides respectively. The higher chlorinated.products, ile., compounds. formed by both addition and substitutionresult when there are used both the higher temperatures and quantitiesof chlorine greater than required stoichiometrically to saturate theolefinic double bonds.

The presently useful chloro-substituted N,N-dialkylstearamides, may alsobe prepared by chlorinating oleic acid, linoleic' acid or technicalmixtures thereof to give dichloroand/or tetrachlorostearic acid, andcondensing said chlorostearicacid. with a dialkylamine having from 1 to5 carbon atoms in the alkylradical.

The presently employed chlorine-substituted N,N-di alkylstearamides arecompletely compatible with vinyl chloride polymers. and show noexudation of plasticizer even at plasticizer content of up to 50percent. Although the quantity of plasticizer will depend upon theparticular polymer to be plasticized and upon its molecular weight, itis generally found that compositions having from 5 percent-to 50 percentby weight of plasticizer will, in most cases, be satisfactory for,generally utility. The good flexibility of, the, plasticizedcompositions. increases with increasingplasticizer concentration.

In evaluating plasticizer efiiciency, use is made of the followingempirical testing procedures:

C0mpatibility.-Visual inspection of the plasticized composition, isemployed, incompatibility of the plasticizer with the polymer beingdemonstrated by; cloudie ness. and exudation of the plasticizer.

Hardness.-A standard instrument made by the Shore Instrument Company isused for this determination and expresses the hardness in units from oneto 100'; The hardnessv of thecomposition is judged by its resistance tothe penetration of a standard needle applied to the composition under astandard road for. a standard length of. time.

Low temperature flexibility-Low temperature flexi bility is one of themost important properties of elastomeric vinyl. compositions. While manyplasticizers Will produce flexible compositions at room temperature theflexibility of these compositions at low temperatures may varyconsiderably, i.e., plasticized polyvinyl chloride compositions that areflexible at room temperature often become very brittle and useless atlow temperatures. Low temperature flexibility tests herein, employedare. according to the Clash-Berg method. This method determines thetorsional flexibility of a plastic at various temperatures. The,temperature at which the vinyl composition exhibits an arbitrarilyestablished minimum flexibility is de-fined as the low temperatureflexibility of the composition. This value may also be defined as thelower temperature limit of the plasticized compositions usefulness as anelastomer.

Volatility.]ust as a decrease in temperature often results in decreasedflexibility of a plasticized polymer composition'so does a decrease inplasticizer concentration when caused by volatilization of theplasticizer. Hence, plasticizers which are readily volatilized from theplasticized composition as a result of aging or heating are inefficientbecause upon volatilization the plasticized composition becomes stiffand hard. The test for plasticizer volatility herein employed is amodified carbonabsorption test of the Society of Plastics Industry.

Water resistance-The amount of water absorption and the amount ofleaching that takes place when the plasticized composition is immersedin distilled water for 24 hours is determined.

The invention is further illustrated, but not limited, by the followingexamples:

Example 1 There was charged to a reaction vessel equipped with a stirrerand provided with gas inlet tube, 154.5 g. (0.5 mole) of theN,N-dimethyl amide of a mixture of higher aliphatic monocarboxylic acidsknown to the trade as Acintol FA No. 2. This mixture of fatty acids isreputed to consist 50 percent by weight of oleic acid, 48 percent byweight of linoleic acid and 2 percent by weight of saturated acids. TheN,N-dimethylamide of the Acintol was prepared in known manner bycondensation with dimethylamine.

The charge of amide was exposed to ultra-violet radiation and 60 g. ofdry chlorine was gradually led into the amide, with constant stirring.During the chlorine addition, an exothermal temperature of from 40-50 C.was noted. When all of the chlorine had been introduced, the reactionvessel was purged with nitrogen. Because the reaction mixture had becomequite viscous, it was then diluted with ether and the diluted materialwaterwashed until neutral. The resulting organic layer was dried andheated to a temperature of 150 C./l mm. to drive oir' the solvent. Therewas thus obtained as residue 198 g. of the chlorinated dimethylamide, n1.4910, analyzing 1.05 percent free acid, calculated as oleic acid,23.93 percent chlorine and 2.99 percent nitrogen. The chlorinatedmaterial contains 2.7 atoms of chlorine per mole of product and is thusa mixture consisting approximately one-half ofN,N-dimethyl-9,IO-dichlorostearamide and one-half ofN,N-dimethyl-9,10,12,13-tetrachlorostearamide.

Example 2 Sixty parts of polyvinyl chloride and 40 parts by weight ofthe chlorinated dimethylamide of Example 1 were mixed on a rolling millto a homogeneous blend. During the milling there was observedsubstantially no fuming or discoloration. A molded sheet of the mixturewas clear and transparent and substantially colorless. Testing of themolded sheet for low temperature flexibility, according to the testingprocedure described above, gave a value of minus 17.4 C., which valuedenotes very good low temperature properties. Tests on the volatilitycharacteristics of the plasticized composition gave a value of 1.7percent which shows very good retention of plasticizer and indicatedgood temperature characteristics of the composition. When subjected toheat at a temperature of 325 F. for a period of 30 minutes the clarityand color of the molded product was substantially unchanged. Tests ofthe water-resistance of the plasticized material showed a solids loss ofonly 0.04 percent and a water absorption value of 0.90 percent.

While the above example shows only a composition in which the ratio ofplasticizer to polymer content is 40:60, this ratio being employed inorder to get comparable efliciencies, the content of chlorinated amidemay be widely varied depending upon the properties desired in the finalproduct. For many purposes a plasticizer content of, say, from only 10percent to 20 percent is preferred. The present chloro dialkylamides arecompatible with polyvinyl chloride over a wide range of concentration,up to 50 percent of amides based on the total weight of the plasticizedcomposition yielding desirable products.

Although the invention has been described particularly with reference tothe use of the present amides as plasticizers for polyvinyl chloride,these compounds are advantageously employed also as plasticizers forcopolymers of vinyl chloride, for example, the copolymers of vinylchloride with vinyl acetate or vinylidene chloride. Preferably, suchcopolymers have a high vinyl chloride content, i.e., a vinyl chloridecontent of at least 70 percent by weight of vinyl chloride and up to 30percent by weight of the copolymerizable monomer.

The plasticized polyvinyl halide compositions of the present inventionhave good thermal stability; in some instances the present chloro-amidesimpart flame-resistance to vinyl chloride polymers. Thechlorine-substituted N,N-dialkylstearamides are of general utility insoftening vinyl chloride polymers. They may be used as the onlyplasticizing component in a compounded vinyl chloride polymer or theymay be used in conjunction with other plasticizers.

This application is a division of my copending application, Serial No.406,070, filed January 25, 1954, and now abandoned.

What I claim is:

1. A resinous composition comprising a polymeric material selected fromthe class consisting of polyvinyl chloride and a copolymer of at least70% by weight of vinyl chloride and up to 30% by weight of vinylacetate, said polymeric material being plasticized with from 5 to 50% byweight, based on the weight of the resinous composition, of a mixture ofchlorine-substituted N,N- dialkylstearamides prepared by thechlorination of an N,N-dialkylamide of tall oil fatty acid fractionhaving from 1 to 5 carbon atoms in each alkyl radical and consistingessentially of an N,N-dialkyl-9,10-dichlorostearamide and anN,N-dialkyl-9,10,12,13-tetrachlorostearamide wherein each alkyl radicalis as herein defined.

2. A resinous composition comprising polyvinyl chloride plasticized withfrom 5 to 50% by weight, based on the weight of the resinouscomposition, of a mixture of chlorine-substituted N,N-dialkylstearamidesprepared by the chlorination of an N,N-dialkyl amide of tall oil fattyacid fraction having from 1 to 5 carbon atoms in each alkyl radical andconsisting essentially of an N,N-dialkyl-9,10-dichlorostearamide and anN,N-dialkyl-9,10,l2- 13-tetrachlorostearamide wherein each alkyl radicalis as herein defined.

3. A resinous composition comprising a copolymer of at least 70% byweight of vinyl chloride and up to 30% by weight of vinyl acetate, saidcopolymer being plasticized with from 5 to 50% by weight, based on theweight of the resinous composition, of a mixture of chlorine-substitutedN,N-dialkylstearamides prepared by the chlorination of an N,N-dialkylamide of tall oil fatty acid fraction having from 1 to 5 carbon atoms ineach alkyl radical and consisting essentially of an N,N-dialkyl-9,10-dichlorostearamide and an N,N-dialkyl-9,l0,12,13-tetrachlorostearamide wherein each alkyl radical is as herein defined.

4. A resinous composition comprising polyvinyl chloride plasticized withfrom 5 to 50% by weight, based on the weight of the resinous compositionof a mixture of chloroamides prepared by the chlorination of theN,N-dimethylamide of tall oil fatty acid fraction and consistingessentially of N,N-dimethyl-9,l0-dichlorostearamide andN,N-dimethyl-9,10,12,1I i-tetrachlorostearamide.

No references cited.

1. A RESINOUS COMPOSITION COMPRISING A POLYMERIC MATERIAL SELECTED FROMTHE CLASS CONSISTING OF POLYVINYL CHLORIDE AND A COPOLYMER OF AT LEAST70% BY WEIGHT OF VINYL CHLORIDE AND UP TO 30% BY WEIGHT OF VINYLACETATE, SAID POLYMERIC MATERIAL BEING PLASTICIZED WITH FROM 5 TO 50% BYWEIGHT, BASED ON THE WEIGHT OF THE RESINOUS COMPOSITION, OF A MIXTURE OFCHLORINE-SUBSTITUTED N,NDIALKYLSTEARAMIDES PREPARED BY THE CHLORINATIONOF AN N,-DIALKYLAMIDE OF TALL OIL FATTY ACID FRACTION HAVING FROM 1 TO 5CARBON ATOMS IN EACH ALKYL RADICAL AND CONSISTING ESSENTIALLY OF ANN,N-DIALKYL-9, 10-DICHLOROSTEARAMIDE AND AN N,N-DIALKYL-9, 10, 12,13-TETRACHLOROSTEARAMIDE WHEREIN EACH ALKYL RADICAL IS AS HEREINDEFINED.